Water-insoluble thiazole and thiadiazole azo dyestuffs

ABSTRACT

Water-insoluble p-aminoazo dyes having a thiadiazole diazo component and an acetoacetoxyalkyl group on the amino nitrogen atom of a p-aminophenyl coupling component which are particularly useful for dyeing cellulose esters and synthetic linear polymers such as polyamides, polyurethanes, polyvinyl chloride or polyesters and which have excellent light and wet fastness and resistance to gas-fume fading.

United States Patent Lange, deceased Oct. 7, 1975 WATER-INSOLUBLETHIAZOLE AND THIADIAZOLE AZO DYESTUFFS Inventor: Guenter Lange,deceased, late of -Ludwigshafen, Germany, by

Elisabeth Hedwig Lange, heiress-at-law Badische Anilin- & Soda-FabrikAktiengesellschaft, Ludwigshafen (Rhine), Germany Filed: May 28, 1971Appl. No.: 148,239

Related US. Application Data Continuation-impart of Ser. No. 828,387,May 27, 1969, Pat. No. 3,658,784.

Assignee:

Foreign Application Priority Data June l, 1968 Germany 1769503 US. Cl260/158; 260/483 Int. Cl. C09L 29/08 Field of Search 260/ 158 [56]References Cited UNITED STATES PATENTS 3,097,198 7/1963 Fishwick et al260/207.l

FOREIGN PATENTS OR APPLICATIONS 1,503,249 l0/l967 France 260/158 PrimaryExaminerI-Ienry R. Jiles Assistant ExaminerRobert W. Ramsuer Attorney,Agent, or FirmJohnston, Keil, Thompson & Shurtleff [57] ABSTRACT 3Claims, No Drawings WATER-INSOLUBLE THIAZOLE AND THIADIAZOLE AZODYESTUFFS This application is a continuation-in-part of US. applicationSer. No. 828,387 filed on May 27, 1969, now US. Pat. No. 3,658,784.

This invention relates to water-insoluble p-aminoazo dyes having theformula (I):

where D is the radical of the formula or Z- R is the radical having theformula or the formula C,,,H ,,,X;

n is one of the integers 2 and 3 m is one of the integers l, 2, 3 and 4;and

X is hydrogen, hydroxy, cyano, methoxy or ethoxy.

Examples of amines or diazo components from which the radical D isderived are:

2-amino-S-phenylthiadiazole-l ,3,4,

Z-amino-S-ethylthiadiazole-1,3,4,

2-amino-5-( 4'-chlorophenyl )-thiadiazolel ,3,4,

2-amino-4-methylmercaptothiadiazole-l ,3,5, and

2-amino-4-carbomethoxyethylmercaptothiadiazole- Examples of radicals Rwhich are different from R are: methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, ,B-hydroxyethyl, ,B-cyanoethyl, B-methoxyethyl,,B-ethoxyethyl, 'y-hydroxypropyl or 'y-methoxypropyl.

Examples of aniline derivatives having the formula where R, R R and Rhave the meanings given above and which are contained in the dyes havingthe formula (I) as coupling components are:

N-( acetoacet-B-hydroxyethyl)-N-methylaniline, N-bis-(acetoacet-B-hydroxyethyl )-aniline, N-( acetoacet-P-hydroxybutyl)-N-ethylaniline, N-( acetoacet-B-hydroxyethyl )-N-B-'cyanoethylaniline, N-( acetoacet-B-hydroxyethyl )-N-B-hydroxyethylaniline, N-( acetoacet-B-hydroxyethyl )-N-B-methoxyethylaniline, N-( acetoacet-B-hydroxyethyl )-N-ethyl-m-toluidine,N-( acetoacet-B-hydroxyethyl )-N-ethyl-mmethoxyaniline,2-methyl-5-ethoxy-N-( acetoacet-B-hydroxyethyl)-N- ethylaniline or N-(acetoacet-B-hydroxyethyl )-N-B-hydroxyethyl-macetylaminoaniline. The newdyes having the formula (I) may be obtained for example by reaction ofdiazo compounds of amines having the formula (III):

D-NH

(III) with coupling components having the formula (ll).

Dyes having the formula (IV):

where D, R, R m, n and X have the meanings given above may also bereacted with compounds which yield the radical Examples of suchcompounds are alkyl acetoacetates, preferably methyl or ethylacetoacetate or particularly diketene.

The new dyes are suitable, particularly in finely divided form, fordyeing and/or printing synthetic and cellulosic fibers such aspolyesters, polyamides, polyurethanes, polyvinyl chloride andparticularly cellulose esters and ethers.

It is advantageous to use mixtures of the dyes according to thisinvention. These mixtures are for example obtained when diazo compoundsof amines having the formula DNH are reacted with a mixture of couplingcomponents having the formula (II) which has been prepared by incompleteacylation of a starting component having the general formula (V):

or when dyes having the formula (IV) are incompletely acylated.Preferred compounds to be acylated are those in which X denotes ahydroxyl group.

The new dyes or dye mixtures give scarlet to blue dyeings which haveexcellent light and wet fastness and which are very resistant togas-fume fading.

The invention is illustrated by the following Examples in which theparts and percentages relate to weight.

EXAMPLE 1 12 parts of 3-carbomethoxyethylmercapto-5- aminothiadiazole-l,2,4 is introduced at from 10 to 15C into a mixture of 30 parts ofsulfuric acid, 50 parts of propionic acid and 50 parts of glacial aceticacid. 15 parts of nitrosylsulfuric acid (12.7 percent of dinitrogentrioxide) is run in slowly and the diazo solution thus prepared isstirred for another 4 hours and then poured into a coupling solutionwhich has been obtained by dissolving 14.5 parts ofN-acetoacet-B-hydroxyethyl-N- [3-cyanoethylaniline in 25 parts ofhydrochloric acid 10 moles per liter) and 100 parts of water followed bythe addition of 700 parts of ice and 200 parts of ice water.

After the diazo solution has been run in, the whole is neutralized with120 parts of caustic soda solution 10 moles per liter) and stirredovernight, and the dye is isolated as usual. 20 parts of a powder isobtained which dyes acetate rayon bright scarlet shades.

EXAMPLE 2 A diazo solution is prepared analogously to Example 1 from 7.3parts of 3-methylmercapto-5- aminothiadiazole-l ,2,4 and is then addedto a coupling solution which has been obtained by dissolving 15 parts ofN-acetoacet-B-hydroxyethyl-N-B-cyanoethyl-mtoluidine in 50 parts ofwater with an addition of 300 parts of .ice and 250 parts of ice water.

After the diazo solution has been added, the whole is neutralized to pH5 with 100 parts of caustic soda solution moles per liter). The productis processed as usual after being stirred overnight. 24 parts of a dyeis obtained which gives bright scarlet dyeings on acetate rayon.

EXAMPLE 3 a 9 parts of 2-amino-S-phenylthiadiazole-1,3,4 is introducedinto a mixture of 50 parts of phosphoric acid, parts of sulfuric acidand 15 parts of nitrosylsulfuric acid (12.7 percent of dinitrogentrioxide). After the diazo solution thus prepared has been stirred forfour hours the diazo solution is added to a coupling solution which hasbeen obtained by dissolving 13.5 parts of N-acetoacet-B-hydroxyethyl-N-ethylaniline in 10 parts of water and 50parts of ice followed by an addition of 600 parts of ice.

When all the diazo solution has been added, the whole is further dilutedwith another 250 parts of ice water and neutralized to a pH value offrom 5 to 6 by adding 140 parts of caustic soda solution (10 moles/-liter). The whole is stirred overnight and the deposited precipitate issuction filtered, washed until neutral with water and dried at 50C atsubatmospheric pressure. 15 parts of a powder is obtained which dyesacetate rayon bright scarlet shades.

Production of the coupling components:

90.5 parts of N-di-,B-hydroxyethylaniline has parts of methylacetoacetate added to it and is then heated first to C and then slowlyto C. The total duration of the heating is 6 hours. 18 parts of methanoldistil over slowly. The whole is then cooled to 80C and a small amount(about 1 part) of unreacted methyl acetoacetate is removed at from 10 to15 mm.

132 parts of a pale oil is obtained which contains N-(acetoacet-B-hydroxyethyl )-l\l-B-hydroxyethylaniline as main productand small amounts of corresponding diester and starting material. Themolecular weight determined from coupling with nitrosamine is 270.

The following coupling components (which contain N-(acetoacet-B-hydroxyethyl )-N-B-hydroxyethyl-mtoluidine orN-(acetoacet-B-hydroxyethyl)-N-B- hydroxyethyl-m-acetaminoaniline asmain product) which are hereinafter described under the name of the mainproduct are obtained in the same way from the appropriate startingmaterials.

Dyes characterized by the diazo and coupling components in the followingTable are obtained by a method analogous to that described in Examples 1to 4.

1n the following Table, the Coupling Components (CC) used are asfollows:

1 N-( acetoacet-B-hydroxyethyl )-N-ethylaniline 2. N-(acetoacet-B-hydroxyethyl )-N- cyanoethylaniline 3.N-(acetoacet-B-hydroxyethyl)-N-cyanoethyl-mtoluidine 4. N-(acetoacet-B-hydroxyethyl )-N- methoxyethylaniline 5. N,N-di-(acetoacet-B-hydroxyethyl )-m-toluidine 6. N-( acetoacet-B-hydroxypropyl)-N- cyanoethylaniline 7.N-(acetoacet-B-hydroxyethyl)-N-benzy1-mtoluidine 8.N-(acetoacet-B-hydroxyethyl)-N-benzylaniline 9. N-(acetoacet-B-hydroxyethyl )-N-ethyl-mtoluidine 10. N-(acetoacet-B-hydroxyethyl )-N-B-hydroxyethyl-m-toluidine l l. N-(acetoacet-B-hydroxyethyl)-N-B-hydroxyethyl-m-acetoaminoaniline 12.N-(acetoacet-B-hydroxyethyl)-N-B-hydroxyethyl-3-chloroaniline 13.N-(acetoacet-B-hydroxyethyl)-N-B- hydroxyethyl-2,S-dimethoxyanilinered 1. A dye having the formula where D is the radical of the formula Yis methyl or carbomethoxyethyl,

Z is ethyl, phenyl or p-chlorophenyl,

R is hydrogen, methyl, ethyl, methoxy r ethoxy;

R is hydrogen, chlorine, methyl, ethyl, methoxy, ethoxy, acetylamino orpropionylamino;

R is the radical having the formula:

R is the radical having the formula n is one of the integers 2 and 3 mis one of the integers l, 2, 3 and 4; and

X is hydrogen, hydroxy, cyano, methoxy or ethoxy.

2. The dye of the formula 3. The dye of the formula c upcocn cocn UNITEDSTATES PATENT OFFICE CERTIFICATE OF CGRRECTION PATENT NO. 3,910,874

DATED October 7, 1975 INVENTOR(5) I Guenter Lange, deceased It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

In Column 6, Claim 1, in the formula after "R is the O O radical havingthe formula: delete "C H -OC-CH CCH and insert C H -OC-CH CCH Signed andgcaled this twenty-second 3 [SEAL] D yof June1976 Attest:

RUTH cmsou QMRSHALLDANN Ane 'trng Ojjrcer I (ommissiuner oj'larenls andTrademarks

1. A DYE HAVING THE FORMULA
 2. The dye of the formula
 3. The dye of theformula